Inspired by the diversity of structures and patterns inherent in the earth's lithosphere, this study endeavors to enhance the interplay between stiffness and toughness through the introduction of a new class of polymeric multi-layer composite materials termed by the authors as "lithomers". Structured single-edge notched bending specimens were fabricated using a combination of additive manufacturing and casting, employing two different methacrylate-thiol resins. The outer layers exhibit a stiff and brittle characteristic, while the layer in between is compliant in nature. Three types of lithomers with wave-like structures and one with a rectilinear structure were investigated regarding their stiffness and toughness in a 3-point bending setup. The results were compared with those of a pure stiff matrix material. The findings revealed that fracture toughness increased regardless of the interlayer's shape compared to the pure matrix material. Correspondingly, this enhancement in fracture toughness correlated with a reduction in stiffness. The most balanced results in terms of stiffness and fracture toughness were achieved, with the lithomer having a wave-like structure in its initial stage. It exhibited a roughly 27 times improvement in fracture toughness with a moderate decrease in stiffness of approx. 1/5 compared to the pure matrix material.